CN116060061B - Vanadium phosphorus oxygen catalyst precursor powder and catalyst prepared from same - Google Patents
Vanadium phosphorus oxygen catalyst precursor powder and catalyst prepared from same Download PDFInfo
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- CN116060061B CN116060061B CN202111278928.2A CN202111278928A CN116060061B CN 116060061 B CN116060061 B CN 116060061B CN 202111278928 A CN202111278928 A CN 202111278928A CN 116060061 B CN116060061 B CN 116060061B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 239000000843 powder Substances 0.000 title claims abstract description 57
- 239000012018 catalyst precursor Substances 0.000 title claims abstract description 43
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 title description 10
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002245 particle Substances 0.000 claims abstract description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 38
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 239000007921 spray Substances 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 238000001694 spray drying Methods 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 39
- 238000002360 preparation method Methods 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
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- 230000003213 activating effect Effects 0.000 claims description 2
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- 230000001590 oxidative effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 4
- 230000000630 rising effect Effects 0.000 abstract description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 24
- 238000003756 stirring Methods 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
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- 239000000725 suspension Substances 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- -1 butane-substituted benzene Chemical class 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 150000001298 alcohols Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides vanadium phosphorus oxide catalyst precursor powder and a catalyst prepared from the vanadium phosphorus oxide catalyst precursor powder, wherein an organic solvent, vanadium pentoxide and phosphoric acid are mixed, the temperature is raised to 90-115 ℃ at a heating rate of 3-20 ℃/h, the reaction is carried out for 4-20 h under the condition of heat preservation, the slurry of the vanadium phosphorus oxide catalyst precursor is obtained, and the slurry is sprayed into a spray granulator for drying and roasting, so that the vanadium phosphorus oxide catalyst precursor is obtained. And then directly carrying out molding activation to obtain the vanadium phosphorus oxide catalyst. The particle size of solid particles in the precursor slurry is less than 150nm by controlling the temperature rising speed, the reaction temperature and the reaction time, so that the catalyst is ensured to have higher pore volume and specific surface area, and the catalyst performance is improved; the slurry with the particle size range is more suitable for spray drying, precursor powder with uniform particles and the size of 0.5-1.5 mu m is formed, the particle size distribution is centralized and controllable, the precursor powder is ensured to have good fluidity and higher bulk density, and the subsequent tabletting and forming are facilitated.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to vanadium phosphorus oxygen catalyst precursor powder and a catalyst prepared from the vanadium phosphorus oxygen catalyst precursor powder.
Background
Maleic anhydride, abbreviated as maleic anhydride, is an important organic chemical raw material for the production of thermosetting resins, unsaturated polyester resins, pesticides and fine chemical products in large quantities, such as important intermediates for the synthesis of gamma-butyrolactone, tetrahydrofuran and 1, 4-butanediol. Previously, benzene was used as a raw material to produce maleic anhydride, but because of benzene toxicity, unsafe properties and environmental hazards, butene was used instead of benzene as a raw material to produce maleic anhydride. However, since butene was expensive, it has gradually turned over to producing maleic anhydride from inexpensive and readily available butane-substituted benzene and butene as raw materials since the 70 s. The process for preparing maleic anhydride by n-butane oxidation has the advantages of low raw material cost, little environmental pollution and low maleic anhydride production cost, and the vanadium-phosphorus-oxygen catalyst is the most effective catalyst for preparing maleic anhydride by n-butane oxidation.
However, the vanadium phosphorus oxygen catalyst is a complex catalyst system, and the preparation method of the vanadium phosphorus oxygen catalyst has great influence on the physicochemical property, structure and catalytic performance of the catalyst. Since the successful commercial application of vanadium phosphorus oxide catalysts, a large number of researchers have conducted intensive research into the process for their preparation. Early catalyst preparation was carried out using water as a solvent, hydrochloric acid (including hydrogen chloride gas), oxalic acid, and the like as reducing agents, and as a result, the obtained catalyst was found to have a smaller specific surface area. The catalyst is prepared in the organic phase later, and the reducing agent is alcohols, esters, aldehydes, etc. The catalyst prepared in the organic phase has larger specific surface area, and the catalytic performance of the catalyst prepared in the organic phase is generally superior to that of the catalyst prepared by taking water as a solvent.
CN106311300A discloses a catalyst for preparing maleic anhydride by butane oxidation and a preparation process thereof, wherein pentavalent vanadium is adopted to react with a reducing agent and a phosphorus compound to form a precursor of the catalyst, and then the precursor of the catalyst is filtered, washed, dried and roasted to obtain the precursor of the catalyst. Because the reducing agent is selected from C1-C10 alkyl alcohol, glycol ether, methoxyethanol, methoxypropanol and dimethylformamide, the solvents are volatile, and particularly, the subsequent operation methods of filtering, washing and drying are adopted, so that the recovery of the solvents is difficult to operate and control.
CN101157048a discloses a high-performance vanadium phosphorus oxide catalyst with nano structure and its preparation method, the method adopts vanadium pentoxide and organic reducer and phosphoric acid to react and synthesize to prepare catalyst precursor, then the precursor is filtered, dried, baked, spray-granulated, formed and activated to obtain the vanadium phosphorus oxide catalyst. According to the method, the purpose of increasing the powder pile is achieved by spraying and granulating the roasted powder, so that on one hand, the whole process is complex, and the preparation cost of the catalyst is increased; on the other hand, the solvent volatilization phenomenon in the drying and roasting process can not be controlled, and the potential risk of environmental pollution exists.
Therefore, the process for preparing the vanadium phosphorus oxide catalyst in the prior art has the problem of complex flow, and in terms of the drying procedure, the drying method in the prior art can cause agglomeration and agglomeration of the catalyst, and the subsequent tabletting forming and activating can be carried out only by the process of crushing and granulating after roasting, so that the post-treatment process is complicated. In addition, the catalyst with small granularity has the advantages of large pore volume and specific surface area, but has the problems of low powder-to-mass ratio and poor fluidity, so that tabletting is difficult and the yield of finished tablets is not ideal. In addition, the prior art also has the problems of potential safety hazard and environmental pollution caused by volatilization of the organic solvent.
Disclosure of Invention
Aiming at the defects, the invention provides vanadium phosphorus oxygen catalyst precursor powder and a catalyst prepared from the vanadium phosphorus oxygen catalyst precursor powder, and the catalyst precursor with uniform powder particle distribution, large powder pile ratio and good fluidity is prepared by adopting the improvement of the particle size control and the drying mode of the precursor in the coprecipitation reaction stage, so that the catalyst precursor is suitable for continuous automatic forming and high-quality catalyst production.
The invention adopts the following technical scheme to realize the technical purposes:
the technical purpose of the first aspect of the invention is to provide a preparation method of vanadium phosphorus oxide catalyst precursor powder, which comprises the following steps: mixing an organic solvent, vanadium pentoxide and phosphoric acid, raising the temperature to 90-115 ℃, preferably 92-105 ℃ at a heating rate of 3-20 ℃/h, preferably 6-15 ℃/h, more preferably 8-12 ℃/h, carrying out heat preservation reaction for 4-20 hours, preferably 10-18 hours, obtaining slurry of the vanadium-phosphorus oxide catalyst precursor, spraying the slurry into a spray granulator, drying, and roasting to obtain the vanadium-phosphorus oxide catalyst precursor.
Further, the operating parameters of the spray granulator are as follows: the inlet temperature is 140-200 ℃, preferably 160-200 ℃, and the outlet temperature is 80-100 ℃. The spray granulator is a centrifugal granulation spray dryer, the rotation speed of an atomizer is 5000-20000 rap/min, and 10000-18000 rap/min is preferable.
In order to avoid volatilization of the organic solvent, the spray granulator is closed, prevents environmental pollution, protects production safety, and recovers the solvent.
Further, the method further comprises the step of adjusting the mass content of solids in the slurry to be 5-30%, preferably 10-25%, before spray drying.
Further, the organic solvent is at least one selected from isobutanol, benzyl alcohol, ethylene glycol, 1, 3-propanediol and 1, 4-butanediol; isobutanol is preferred. The weight ratio of the organic solvent to the vanadium pentoxide is 9:1-30:1. The concentration of phosphoric acid is generally more than 85wt%, preferably more than or equal to 100 wt% of concentrated phosphoric acid, and can also be more than 95 wt% of pyrophosphoric acid. The addition amount of phosphoric acid is 0.75-1.40, preferably 0.95-1.2, based on the mole ratio of phosphorus to vanadium.
Further, the roasting temperature is 170-260 ℃, preferably 190-240 ℃ and the roasting time is 3-10 hours.
Further, in the above preparation method, the method further comprises a step of introducing an auxiliary agent. The auxiliary agent is at least one selected from Li, na, K, ca, mg, zn, fe, bi, ni, si, mo, co, zr, cu, ti, la, nb, B, cr or Ce elements. Adding the salts containing the auxiliary elements and the reaction raw materials into the reaction solution.
In the preparation method, the temperature rising speed, the reaction temperature and the reaction time are controlled to ensure that the particle size of solid particles in the vanadium phosphorus oxide catalyst precursor slurry is less than 150nm, under a preferable technical scheme, the particle size of the solid particles is less than 130nm, under a more preferable technical scheme, the particle size of the solid particles is less than 100nm, under a most preferable technical scheme, the particle size of the solid particles is less than 80nm, and the quantity ratio of the particle sizes of the solid particles to the solid particles is more than 85 percent. The smaller solid particles can enable the catalyst to have higher pore volume and specific surface area, and improve the catalyst performance.
In the preparation method, after being dried by a spray granulator, precursor powder with the particle size of 0.5-1.5 mu m, preferably 0.7-1.1 mu m, can be formed, has good fluidity and higher apparent density of 70-115 g/cm 3, preferably 90-110 g/cm 3, is beneficial to subsequent tabletting and forming, and can obtain higher catalyst preparation efficiency.
The technical purpose of the second aspect of the invention is to provide vanadium phosphorus oxide catalyst precursor powder prepared by the method. The particle size of the precursor powder is 0.5-1.5 mu m, preferably 0.7-1.1 mu m, and the precursor powder has higher apparent density of 70-115 g/cm 3, preferably 90-110 g/cm 3.
The technical purpose of the third aspect of the invention is to provide a preparation method of the vanadium phosphorus oxide catalyst, which is obtained by directly performing molding activation on the vanadium phosphorus oxide catalyst precursor powder.
In the preparation process of the vanadium phosphorus oxide catalyst in the prior art, generally, after the vanadium phosphorus oxide catalyst precursor slurry is obtained by a coprecipitation method, a filter cake is obtained by filtering, and after drying (generally vacuum drying or air drying) and roasting, the obtained precursor is a conglomerate body, and before tabletting, the requirement of subsequent tabletting can be met by a crushing and granulating process, while the precursor powder has a particle size of 0.5-1.5 mu m, has higher apparent density, can be directly subjected to tabletting and shaping, and greatly reduces the post-treatment process.
Further, in the preparation method of the catalyst, the method further comprises the step of introducing an auxiliary agent. The auxiliary agent is at least one selected from Li, na, K, ca, mg, zn, fe, bi, ni, si, mo, co, zr, cu, ti, la, nb, B, cr or Ce elements. The promoter is introduced into the catalyst in one of the following ways: (1) Introducing the vanadium phosphorus oxide precursor into a reaction solution in the preparation process of the vanadium phosphorus oxide precursor; (2) introduced prior to or during the shaping of the catalyst; preferably in the reaction solution during the preparation of the vanadium phosphorus oxide precursor.
Further, the molding method can be a conventional molding method in the catalyst field such as sheeting, extruding or balling. The shape of the prepared formed catalyst can be bar shape, clover shape, raschig ring, tooth ball, honeycomb or open-pore cylinder shape.
Further, the activation is performed under the atmosphere of one or a combination of more than one of air/inert gas, air/butane, air/water vapor and butane/inert gas mixture. The activation temperature is generally 260 to 450 ℃, preferably 370 to 430 ℃, and the activation time is generally 3 to 30 hours, preferably 6 to 24 hours.
The technical object of the fourth aspect of the invention is to provide a vanadium phosphorus oxide catalyst prepared by the method. The vanadium phosphorus oxide catalyst prepared by the method has higher specific surface area and pore volume and good catalyst performance.
The technical purpose of the fifth aspect of the invention is to provide a method for preparing maleic anhydride by oxidizing n-butane, wherein the method is catalyzed by the vanadium phosphorus oxide catalyst and adopts a fixed bed, moving bed or fluidized bed reaction mode, and the reaction conditions are as follows: the temperature is 375-445 ℃, the pressure is normal pressure to 0.5MPa, the space velocity of the n-butane mixed gas is 800-2800 h -1, and the n-butane concentration is 1.0-1.8% (volume percent).
Compared with the prior art, the invention has the following advantages:
(1) In the preparation process of the vanadium phosphorus oxide catalyst precursor powder, the particle size of solid particles in the vanadium phosphorus oxide catalyst precursor slurry is less than 150nm by controlling the temperature rising speed, the reaction temperature and the reaction time, so that the catalyst is ensured to have higher pore volume and specific surface area, and the catalyst performance is improved; the slurry with the particle size range is more suitable for spray drying to form precursor powder with uniform particles and the size of 0.5-1.5 mu m, the particle size distribution is centralized and controllable, the precursor powder is ensured to have good fluidity and higher bulk density, the subsequent tabletting forming is facilitated, the continuous automatic catalyst forming is suitable, and the higher catalyst preparation efficiency is obtained.
(2) The preparation method of the precursor can save the technical processes of filtering, crushing and granulating in the prior art, shortens the preparation flow of the catalyst, and effectively solves the problems of difficult drying and low drying efficiency of the vanadium phosphorus oxide catalyst.
(3) The preparation method saves the process flow, is easy to control the process, is suitable for mass production of high-quality catalysts, and has important significance for the industrial production of the catalysts.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
In the following examples and comparative examples, the laser particle sizer used for powder particle size measurement was a Mastersizer 2000 particle sizer, uk; the loose density test method comprises the following steps: uniformly dropping powder from a hopper according to a certain height, filling a measuring cylinder to a certain scale mark in a loose state, weighing the mass of the powder, and representing the loose density of the powder by using the mass of the loose powder in unit volume; the specific surface area was measured using an AUT0S0RB3B full-automatic specific surface area and pore size distribution instrument from Quantachrome, inc. of America.
In examples 1-4, vanadium phosphorus oxide catalyst precursor powders were prepared according to the method of the present invention:
Example 1
A four-neck flask with a stirring and reflux cooling device is adopted, 960g of isobutanol, 50.0g of vanadium pentoxide and 0.4g of auxiliary agent calcium hydrophosphate are added into the four-neck flask, then 80.0g of concentrated phosphoric acid with the concentration of 95% is added, stirring is started, the rotation number is 600r/min, the reaction temperature is gradually increased to 94 ℃ at the heating rate of 10 ℃/h, the temperature is kept for 10 hours, the blue slurry suspension of the vanadium-phosphorus oxide catalyst precursor is obtained, the solid content is 16.0%, and the particle size of solid particles is 92% in the range of 40-100 nm. And then spraying the slurry into a centrifugal granulating spray dryer, wherein the inlet temperature is 200 ℃, the outlet temperature is 100 ℃, the rotating speed of an atomizer is 18000rap/min, and the obtained spray granulating powder is roasted for 6 hours at 230 ℃ to obtain vanadium phosphorus oxide catalyst precursor powder A1.
Example 2
A four-neck flask with a stirring and reflux cooling device is adopted, 1040g of isobutanol, 100.0g of vanadium pentoxide and 0.06g of auxiliary ferric sulfate are added into the four-neck flask, then 130.0g of concentrated phosphoric acid with the concentration of 100% is added, stirring is started, the rotation number is 800r/min, the reaction temperature is gradually increased to 97 ℃ at the heating rate of 8 ℃/h, the temperature is kept for 12 hours, the blue slurry suspension of the vanadium-phosphorus oxide catalyst precursor is obtained, the solid content is determined to be 25.2%, and the particle size of solid particles is 90% in the range of 40-100 nm. And then spraying the slurry into a centrifugal granulating spray dryer, wherein the inlet temperature is 180 ℃, the outlet temperature is 80 ℃, the rotation speed of an atomizer is 12000rap/min, and the obtained spray granulating powder is roasted for 4 hours at 240 ℃ to obtain vanadium phosphorus oxide catalyst precursor powder A2.
Example 3
A four-neck flask with a stirring and reflux cooling device is adopted, 900g of isobutanol and 75.0g of vanadium pentoxide are added into the four-neck flask, then 108.5g of concentrated phosphoric acid with the concentration of 105% is added, stirring is started, the revolution is 700r/min, the reaction temperature is gradually increased to 101 ℃ at the heating rate of 12 ℃/h, the temperature is kept for 18 hours, the blue slurry suspension of the vanadium-phosphorus oxide catalyst precursor is obtained, the solid content is 20.5%, and the particle size of solid particles is 88% in the ratio between 40 nm and 100 nm. And then spraying the slurry into a centrifugal granulating spray dryer, wherein the inlet temperature is 200 ℃, the outlet temperature is 80 ℃, the rotation speed of an atomizer is 16000rap/min, and the obtained spray granulating powder is roasted for 6 hours at 220 ℃ to obtain vanadium phosphorus oxide catalyst precursor powder A3.
Example 4
A four-neck flask with a stirring and reflux cooling device is adopted, 1200g of isobutanol and 75.0g of vanadium pentoxide are added into the four-neck flask, then 99.0g of concentrated phosphoric acid with the concentration of 115% is added, stirring is started, the revolution is 600r/min, the reaction temperature is gradually increased to 105 ℃ at the heating rate of 10 ℃/h, the temperature is kept for 14 hours, the blue slurry suspension of the vanadium-phosphorus oxide catalyst precursor is obtained, the solid content is determined to be 18.3%, and the particle size of solid particles is determined to be 86% in the range of 40-100 nm. And then spraying the slurry into a centrifugal granulating spray dryer, wherein the inlet temperature is 160 ℃, the outlet temperature is 90 ℃, the rotation speed of an atomizer is 10000rap/min, and the obtained spray granulating powder is roasted for 5 hours at 240 ℃ to obtain vanadium phosphorus oxide catalyst precursor powder A4.
Comparative example 1
75.0G of vanadium pentoxide was added to 1200g of isobutanol, followed by 99.0g of 115% strength concentrated phosphoric acid, stirring was started at 600r/min, the reaction temperature was 105℃and the coprecipitation reaction was carried out for 14 hours. And (3) reducing the reaction product to room temperature, performing vacuum suction filtration, washing a filter cake in the suction filtration process with isobutanol four times, naturally air-drying the filter cake at room temperature, then placing the filter cake in an oven, drying at 120 ℃ for 8 hours, finally roasting the solid product at 250 ℃ for 8 hours, wherein the powder agglomeration phenomenon is serious, and performing crushing and then reconstructing to obtain vanadium phosphorus oxide powder B1.
Comparative example 2
50.0G of vanadium pentoxide is added into 960g of isobutanol, then 0.4g of auxiliary agent calcium hydrophosphate is added, a stirring paddle is started, the revolution is 600r/min, then 80.0g of concentrated phosphoric acid with the concentration of 95% is added, the reaction temperature is 94 ℃, the coprecipitation reaction is carried out, and the reaction time is controlled to be 10 hours, and then the process is finished. And (3) reducing the reaction product to room temperature, performing vacuum suction filtration, washing a filter cake in the suction filtration process with isobutanol four times, naturally air-drying the filter cake at room temperature, then placing the filter cake in an oven, drying the filter cake at 120 ℃ for 8 hours, finally roasting the solid product at 250 ℃ for 6 hours, wherein the powder agglomeration phenomenon is serious, and performing crushing and then reconstructing to obtain vanadium-phosphorus oxide powder B2.
Comparative example 3
900G of isobutanol and 75.0g of vanadium pentoxide are added into a four-necked flask, 108.5g of concentrated phosphoric acid with the concentration of 105% is added, the stirring revolution is 700r/min, the coprecipitation reaction is carried out for 18 hours at the reaction temperature of 101 ℃ to obtain blue slurry suspension of vanadium phosphorus oxide catalyst precursor, and the particle size of solid particles is measured to be 90-160nm and the proportion is 80%. And then spraying the slurry into a centrifugal granulating spray dryer, wherein the inlet temperature is 200 ℃, the outlet temperature is 80 ℃, the rotation speed of an atomizer is 16000rap/min, and the obtained spray granulating powder is roasted for 6 hours at 220 ℃ to obtain vanadium phosphorus oxide catalyst precursor powder B3.
Comparative example 4
1040G of isobutanol, 100.0g of vanadium pentoxide and 0.06g of auxiliary ferric sulfate are added into a four-necked flask, 130.0g of concentrated phosphoric acid with the concentration of 100% is added, the stirring revolution is 800r/min, the reaction temperature is gradually increased to 97 ℃ at the heating rate of 8 ℃/h, the temperature is kept for 12 hours, the blue slurry suspension of the vanadium-phosphorus-oxygen catalyst precursor is obtained, the solid content is 25.2%, and the particle size of solid particles is 40-100nm and accounts for 90% according to the measurement. And then spraying the slurry into a centrifugal granulating spray dryer, wherein the inlet temperature is 130 ℃, the outlet temperature is 60 ℃, the rotating speed of an atomizer is 4000rap/min, and the obtained spray granulating powder is roasted for 4 hours at 240 ℃ to obtain vanadium phosphorus oxide catalyst precursor powder A2.
The powders prepared in the above examples and comparative examples were subjected to an average particle size measurement and a loose-fill density test, and the results are shown in table 1.
Table 1.
As shown in Table 1, the average particle size and bulk density of the vanadium phosphorus oxide catalyst precursor powders prepared in examples 1 to 4 are far greater than those of the materials in comparative examples, and the flowability and the automatic forming ability of the powders are obviously improved.
Determination of maleic anhydride preparation reaction performance by n-butane oxidation:
The precursor powders prepared in the examples and the comparative examples are extruded into cylindrical catalysts by a rotary tablet press and activated to obtain finished catalysts, and the numbers of the finished catalysts are the same as the numbers of vanadium phosphorus oxides. The specific surface area and pore volume distribution results of the finished catalysts prepared in the examples and comparative examples are given in table 2. Subsequently, the vanadium phosphorus oxide catalyst prepared above was charged into a fixed bed reactor, a reaction mixture gas was introduced, and the composition of the reaction product was analyzed by gas chromatography. The reaction conditions were specifically evaluated as follows: the catalyst particles with 10-20 meshes are sieved after crushing the obtained catalyst and are placed in a reaction tube of a small reactor, and the activity evaluation conditions of all the catalysts are as follows: the reaction temperature is 395 ℃, the reaction pressure is 0.10MPa, the raw material is 1.5% of n-butane/air mixture, and the volume space velocity is 1800h -1. After the device was stably operated for 2 hours, the reaction product was subjected to gas chromatography analysis, and the activity evaluation results are shown in Table 2.
TABLE 2
Claims (19)
1. A preparation method of vanadium phosphorus oxide catalyst precursor powder comprises the following steps: mixing an organic solvent, vanadium pentoxide and phosphoric acid, raising the temperature to 90-115 ℃ at a heating rate of 3-20 ℃/h, and carrying out heat preservation reaction for 4-20 h to obtain slurry of vanadium phosphorus oxide catalyst precursor, spraying the slurry into a spray granulator for drying, wherein the operation parameters of the spray granulator are as follows: and roasting at the inlet temperature of 140-200 ℃ and the outlet temperature of 80-100 ℃ to obtain the vanadium phosphorus oxide catalyst precursor.
2. The preparation method of claim 1, wherein the temperature rise rate after mixing the organic solvent, the vanadium pentoxide and the phosphoric acid is 6-15 ℃/h.
3. The preparation method of claim 2, wherein the temperature rise rate after mixing the organic solvent, the vanadium pentoxide and the phosphoric acid is 8-12 ℃/h.
4. The preparation method according to claim 1, wherein the organic solvent, vanadium pentoxide and phosphoric acid are mixed and then heated to 92-105 ℃.
5. The preparation method of claim 1, wherein the organic solvent, the vanadium pentoxide and the phosphoric acid are mixed, and the reaction is carried out for 10-18 hours under heat preservation.
6. The method according to claim 1, wherein the inlet temperature of the spray granulator is 160-200 ℃.
7. The preparation method of claim 1, wherein the spray granulator is a centrifugal granulation spray dryer, and the rotation speed of an atomizer is 5000-20000 rap/min.
8. The method according to claim 1, further comprising the step of adjusting the mass content of solids in the slurry to 5-30% before spray drying.
9. The method according to claim 8, further comprising the step of adjusting the mass content of solids in the slurry to 10-25% before spray drying.
10. The method according to claim 1, wherein the precursor powder having a particle size of 0.5 μm to 1.5 μm is formed after drying by a spray granulator.
11. The method of claim 10, wherein the precursor powder is dried in a spray granulator to form a bulk density of 70 to 110g/cm 3.
12. The method of claim 1, further comprising the step of introducing an auxiliary agent selected from at least one of Li, na, K, ca, mg, zn, fe, bi, ni, si, mo, co, zr, cu, ti, la, nb, B, cr or Ce elements; adding the salts containing the auxiliary elements and the reaction raw materials into the reaction solution.
13. Vanadium phosphorus oxide catalyst precursor powder prepared by the process of any one of claims 1-12.
14. The vanadium phosphorus oxide catalyst precursor powder according to claim 13, wherein the particle diameter is 0.5 μm to 1.5 μm and the bulk density is 70 to 115g/cm 3.
15. The vanadium phosphorus oxide catalyst precursor powder according to claim 14, wherein the particle diameter is 0.7 μm to 1.1 μm and the bulk density is 90 to 110g/cm 3.
16. A method for preparing a vanadium phosphorus oxide catalyst, which is obtained by directly molding and activating the vanadium phosphorus oxide catalyst precursor powder of claim 13.
17. The method of claim 16, further comprising the step of introducing an auxiliary agent selected from at least one of Li, na, K, ca, mg, zn, fe, bi, ni, si, mo, co, zr, cu, ti, la, nb, B, cr or Ce elements; the promoter is introduced into the catalyst in one of the following ways: (1) Introducing the vanadium phosphorus oxide precursor into a reaction solution in the preparation process of the vanadium phosphorus oxide precursor; (2) introduced prior to or during the shaping of the catalyst.
18. The vanadium phosphorus oxide catalyst prepared by the method of claim 16.
19. A method for preparing maleic anhydride by oxidizing n-butane, which uses the vanadium phosphorus oxide catalyst as set forth in claim 18 for catalytic reaction.
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